IVAS 2022 banner
IVES 9 IVES Conference Series 9 IVAS 9 IVAS 2022 9 Hemisynthesis, NMR Characterization and UHPLC-Q-Orbitrap /MS² identification of (+)-Catechin oxidation products in red wines and grape seed extracts

Hemisynthesis, NMR Characterization and UHPLC-Q-Orbitrap /MS² identification of (+)-Catechin oxidation products in red wines and grape seed extracts

Abstract

(+)-Catechin—laccase oxidation dimeric standards were hemi-synthesized using laccase from Trametes versicolor in a water-ethanol solution at pH 3.6. Eight fractions corresponding to eight potential oxidation dimeric products were detected. The fractions profiles were compared with profiles obtained with two other oxidoreductases: polyphenoloxidase extracted from grapes and laccase from Botrytis cinerea. The profiles were very similar, although some minor differences suggested possible dissimilarities in the reactivity of these enzymes. Five fractions were then isolated and analyzed by 1D and 2D NMR spectroscopy. The addition of traces of cadmium nitrate in the samples solubilized in acetone-d6 led to fully resolved NMR signals of phenolic protons, allowing the unambiguous structural determination of six reaction products, one of the fractions containing two enantiomers. These products were then analyzed in grape seed extracts and red wines (UHPLC-Q-Orbitrap MS). The different dimers had different fragmentation patterns according to their interflavan linkage position. Oxidation dimeric compounds had a specific fragment ion at m/z 393, missing for B-Type dimers fragmentations. A fragment ion at m/z 291 occurred and was specific for oxidation dimeric compounds with a C-O-C linkage. Higher level oxidation products had abundant specific fragments: m/z 425, 397 and 245. These fragmentations were useful to identify them in complex samples such as grape seed extracts and wines. Three grape varieties and three ripening stages were selected and the corresponding seed extracts were obtained. The analyses revealed an increasing trend for the oxidation markers during grape ripening. The analysis of Syrah wines (2018, 2014, 2010) showed a decreasing trend of these molecules during wine ageing which might be due to further oxidation.

DOI:

Publication date: June 23, 2022

Issue: IVAS 2022

Type: Article

Authors

Saucier Cedric1, Deshaies Stacy1, Le Guernevé Christine1,2, Sommerer Nicolas1,2, Garcia Lucas Suc François1, Mouls Laetitia1

1SPO, Université de Montpellier, INRAE, Institut Agro, UMR SPO, Faculté de Pharmacie, 15 avenue Charles Flahault, 34000 Montpellier, France
2INRAE, PROBE Research Infrastructure, PFP Polyphenol Facility, 34060 Montpellier, France

Contact the author

Keywords

wine, grape, polyphenol,oxidation, catechin

Tags

IVAS 2022 | IVES Conference Series

Citation

Related articles…

First step in the preparation of a soil map of the Protected Designation of Origin Valdepeñas (Central, Spain)

This work is a first step to make a map of vineyard soils. The characterization of the soils of the Protected Designation of Origin (D.P.O.) Valdepeñas will allow to group the studied profiles according to their physico-chemical characteristics and the concentrations of most relevant chemical elements. 90 soil profiles were analysed throughout the territory and the soils were sampled and described according to FAO (2006) and classified according to and Soil Taxonomy (2014). All samples were air dried, sieved and some physico-chemical parameters were determined following standard protocols. Also, major and trace elements were analysed by X-ray fluorescence. The statistically study was made using the SPSS program. Trend maps were made using the ArcGIS program. The studied soils have the following average properties: pH, 8.3; electrical conductivity, 0,20 dS/m (low); clay, 18.8% (medium) and CaCO3, 17.1% (high). In the study for the major elements. The major elements of these soils are Si, followed by Ca and Al, with an average content of 203.7 g/kg, 105.5 g/kg and 74.0 g/kg respectively. On the other hand, 27 trace elements have been studied. Of all of them, it can be highlighted the average values of Ba (361.8 mg/kg), Sr (129.3 mg/kg), Rb (83.4 mg/kg), V (74.2 mg/kg) and Ce (70.6 mg/kg). Ba, V and Ce values are higher and the values of Sr and Rb are lower to those found in the literature. The discriminant analysis shows a percentage of grouping of 91%. The content of chemical elements together with the physico-chemical characteristics allows grouping the soils in 4 group according to their order in the classification to Soil Taxonomy; due to the importance of the Calcisols in Castilla-La Mancha, it has been decided to establish them as their own group even if they do not appear in Soil Taxonomy classification.

Grape must quality and mesoclimatic variability in Fruška Gora wine-growing region, Serbia

The Fruška Gora mountain is a traditional wine-growing region in Serbia situated in the Pannonian Basin. Due to such a position, the vicinity of the Danube River and the presence of concave configuration, it is suitable for grape production. This paper provides analyses of spatial variations in meteorological parameters and grape juice quality within Fruška Gora wine region over three consecutive vintages (2018-2020). The examined period can be defined as warm with cool nights during September (AVG 18,9°C; GDD 1918°C; CI 12°CF) and with the presence of mesoclimatic variability. The East part of the study area was somewhat drier and hotter compared to other parts of the region. The analyses of grape must samples (190 in total) of five cultivars (Cabernet-Sauvignon, Merlot, Chardonnay, Sauvignon blanc and Grašac (Welschriesling)) commonly grown across the region (19 sites), were performed using Fourier Transform Infrared Technology (FTIR). Among all cultivars, Sauvignon blanc was harvested first in the East area (DOY=246±5, GDD at harvest=1552±74, 22.2±0.7 °Brix), while the latest harvest was recorded for Cabernet-Sauvignon in the West (DOY=283±5, GDD at harvest=1936±187, 23.4±1.0 °Brix ). Both the red and white cultivars had higher acidity and YAN in the grape must if the vines were grown in the North and East compared to South and West areas. According to PCA analysis, Grašac showed the lowest variation in grape must chemical composition. Thus, the results confirm that Grašac is the most stable cultivar in Fruška Gora. All monitored cultivars reached technological fruit ripeness by the end of the growing season. However, it was difficult to reach full ripeness of red cultivars, mostly beacuse of uncoupling of technolocical and phenolic ripeness. Thus, Cabernet-Sauvignon had higher variations in GDD sums at harvest compared to other cultivars, which probably increased variations in grape must quality.

The combined effects of climate, soils, and deficit irrigation on yield and quality of Touriga Nacional under high atmospheric demand in the Douro Region

Global warming is one of the biggest environmental, social and economic threats in several viticultural regions. In the Douro Valley, changes are expected in the coming years, namely an increase in temperature and a decrease in precipitation. These changes are likely to have consequences for the production and quality of wine.
The aim of this study was to explore the effects of different soil characteristics combined with several deficit irrigation strategies, managed throughout ETc references and predawn leaf water potentials thresholds, on physiology, yield, and qualitative attributes on the Touriga Nacional variety under years of mild to severe water and heat stress.
The studies were conducted over seven years (2015 to 2021) in two plots of a commercial vineyard located at Quinta do Ataíde (Symington Family Estates) planted in 2011 and 2014 at 170 meters elevation, growing under three water regimes: non-irrigated (NI) and two deficit irrigation strategies (30% and 60% ETc) assessed weekly by Ψpd. The site has an annual rainfall below 500 mm, with high atmospheric demand. Climate data was collected from a weather station, located on site. Berry ripening was followed weekly for fruit analysis. At harvest, yield, vigour and pruning weight per vine were determined from 90 vines by treatment. Each season at veraison the NDVI Index was accessed by a drone. The soils physic-chemistry in the experimental blocs were analysed and grouped by SWHC. Delta C-13 analyses were also performed per treatment in two years.Irrigation had a positive effect on yield per vine, mostly due to an increase in berry and cluster weight, and fertility index through the years. A significant increase in sugar content, colour and phenols was observed with deficit irrigation in some years, but vine vigour related to soil characteristics had by far the greatest impact on quality.

Frost risk projections in a changing climate are highly sensitive in time and space to frost modelling approaches

Late spring frost is a major challenge for various winegrowing regions across the world, its occurrence often leading to important yield losses and/or plant failure. Despite a significant increase in minimum temperatures worldwide, the spatial and temporal evolution of spring frost risk under a warmer climate remains largely uncertain. Recent projections of spring frost risk for viticulture in Europe throughout the 21st century show that its evolution strongly depends on the model approach used to simulate budburst. Furthermore, the frost damage modelling methods used in these projections are usually not assessed through comparison to field observations and/or frost damage reports.
The present study aims at comparing frost risk projections simulated using six spring frost models based on two approaches: a) models considering a fixed damage threshold after the predicted budburst date (e.g BRIN, Smoothed-Utah, Growing Degree Days, Fenovitis) and b) models considering a dynamic frost sensitivity threshold based on the predicted grapevine winter/spring dehardening process (e.g. Ferguson model). The capability of each model to simulate an actual frost event for the Vitis vinifera cv. Chadonnay B was previously assessed by comparing simulated cold thermal stress to reports of events with frost damage in Chablis, the northernmost winegrowing region of Burgundy. Models exhibited scores of κ > 0.65 when reproducing the frost/non-frost damage years and an accuracy ranging from 0.82 to 0.90.
Spring frost risk projections throughout the 21st century were performed for all winegrowing subregions of Bourgogne-Franche-Comté under two CMIP5 concentration pathways (4.5 and 8.5) using statistically downscaled 8×8 km daily air temperature and humidity of 13 climate models. Contrasting results with region-specific spring frost risk trends were observed. Three out of five models show a decrease in the frequency of frost years across the whole study area while the other two show an increase that is more or less pronounced depending on winegrowing subregion. Our findings indicate that the lack of accuracy in grapevine budburst and dehardening models makes climate projections of spring frost risk highly uncertain for grapevine cultivation regions.

Different soil types and relief influence the quality of Merlot grapes in a relatively small area in the Vipava Valley (Slovenia) in relation to the vine water status

Besides location and microclimatic conditions, soil plays an important role in the quality of grapes and wine. Soil properties influence…